Mn‐Cr isotope systematics of the D'Orbigny angrite

Abstract— We have conducted a detailed study of the Mn‐Cr systematics of the angrite D'Orbigny. Here, we report Cr isotopic abundances and Mn/Cr ratios in olivine, pyroxene, glass, chromite, and bulk rock samples from D'Orbigny. ⁵³Cr excesses in these samples correlate well with their respective Mn/Cr ratios and define an isochron with a slope that corresponds to an initial ⁵³Mn/⁵⁵Mn ratio = (3.24 ± 0.04) × 10^?6 and initial ⁵³Cr/⁵²Cr ratio of ?(53) = 0.30 ± 0.03 at the time of isotopic closure. The ⁵³Mn/⁵⁵Mn ratio of the D'Orbigny bulk rock is more than two‐fold the ⁵³Mn/⁵⁵Mn ratio of the angrites Lewis Cliff 86010 (LEW) and Angra dos Reis (ADOR) and implies an older Mn‐Cr age of 4562.9 ± 0.6 Ma for D'Orbigny relative to a Pb‐Pb age of 4557.8 ± 0.5 Ma for LEW and ADOR. One of the most unusual aspects of D'Orbigny is the presence of glass, a phase that has not been identified in any of the other angrites. The Mn‐Cr data for glass and a pyroxene fraction found in druses indicate that they formed contemporaneously with the main phases of the meteorite. Since the Mn‐Cr age of D'Orbigny is ?5 Ma years older than the angrites LEW and ADOR, D'Orbigny likely represents an earlier stage in the evolution of the angrite parent body.     

Petrology and geochemistry of D'Orbigny,geochemistry of Sahara 99555, and the origin of angrites

Abstract— We have done a detailed petrologic study of the angrite, D'Orbigny, and geochemical study of it and Sahara 99555. D'Orbigny is an igneous‐textured rock composed of Ca‐rich olivine, Al‐Ti‐diopside‐hedenbergite, subcalcic kirschsteinite, two generations of hercynitic spinel and anorthite, with the mesostasis phases ulvöspinel, Ca‐phosphate, a silico‐phosphate phase and Fe‐sulfide. We report an unknown Fe‐Ca‐Al‐Ti‐silicate phase in the mesostasis not previously found in angrites. One hercynitic spinel is a large, rounded homogeneous grain of a different composition than the euhedral and zoned grains. We believe the former is a xenocryst, the first such described from angrites. The mafic phases are highly zoned; mg# of cores for olivine are ?64, and for clinopyroxene ?58, and both are zoned to Mg‐free rims. The Ca content of olivine increases with decreasing mg#, until olivine with ?20 mol% Ca is overgrown by subcalcic kirschsteinite with about 30–35 mol% Ca. Detailed zoning sequences in olivine‐subcalcic kirschsteinite and clinopyroxene show slight compositional reversals. There is no mineralogic control that can explain these reversals, and we believe they were likely caused by local additions of more primitive melt during crystallization of D'Orbigny. D'Orbigny is the most ferroan angrite with a bulk rock mg# of 32. Compositionally, it is virtually identical to Sahara 99555; they are the first set of compositionally identical angrites. Comparison with the other angrites shows that there is no simple petrogenetic sequence, partial melting with or without fractional crystallization, that can explain the angrite suite. Angra dos Reis remains an anomalous angrite. Angrites show no evidence for the brecciation, shock, impact metamorphism, or thermal metamorphism that affected the howardite, eucrite, diogenite (HED) suite and ordinary chondrites. This suggests that the angrite parent body may have followed a fundamentally different evolutionary path than did these other parent bodies.     

Isotopic composition of carbon and nitrogen in ureilitic fragments of the Almahata Sitta meteorite

This study characterizes carbon and nitrogen abundances and isotopic compositions in ureilitic fragments of Almahata Sitta. Ureilites are carbon‐rich (containing up to 7 wt% C) and were formed early in solar system history, thus the origin of carbon in ureilites has significance for the origin of solar system carbon. These samples were collected soon after they fell, so they are among the freshest ureilite samples available and were analyzed using stepped combustion mass spectrometry. They contained 1.2–2.3 wt% carbon; most showed the major carbon release at temperatures of 600–700 °C with peak values of δ¹³C from ?7.3 to +0.4‰, similar to literature values for unbrecciated (“monomict”) ureilites. They also contained a minor low temperature (≤500 °C) component (δ¹³C = ca ?25‰). Bulk nitrogen contents (9.4–27 ppm) resemble those of unbrecciated ureilites, with major releases mostly occurring at 600–750 °C. A significant lower temperature release of nitrogen occurred in all samples. Main release δ¹⁵N values of ?53 to ?94‰ fall within the range reported for diamond separates and acid residues from ureilites, and identify an isotopically primordial nitrogen component. However, they differ from common polymict ureilites which are more nitrogen‐rich and isotopically heavier. Thus, although the parent asteroid 2008TC₃ was undoubtedly a polymict ureilite breccia, this cannot be deduced from an isotopic study of individual ureilite fragments. The combined main release δ¹³C and δ¹⁵N values do not overlap the fields for carbonaceous or enstatite chondrites, suggesting that carbon in ureilites was not derived from these sources.     

Search for solar-type nitrogen in the gas-rich Pesyanoe meteorite

Abstract— We report nitrogen isotopic data obtained from a stepwise gas release of two grain-size fractions of the gas-rich meteorite Pesyanoe. Cosmic-ray-produced ¹⁵N_c may be present in all temperature steps ≥600 °C, and we correct this component using spallation ²¹Ne data. The resulting ratios reveal the presence of more than one trapped N component. Indigenous N is released above 1000 °C with an isotopic signature of δ¹⁵N = ?33‰. This is consistent with the rather uniform signatures of indigenous nitrogen in enstatite meteorites. There is no evidence for the presence of “very light” N of δ¹⁵N ? ?200‰. On the other hand, a “heavy” nitrogen component appears in the temperature range 700–800 °C, and coincides with a major release of solar-type noble gases. For a two-component mixture, the isotopic shifts in this temperature range define a lower limit δ¹⁵N_corr = ?6‰ for the second component (e.g., solar-type nitrogen). However, for the case of a solar-type component, the calculated δ¹⁵N signature depends on the adopted elemental abundances. For example, adoption of the relative abundances of ¹⁴N and noble gases in lunar ilmenite 71501 yields δ¹⁵N ? +170, which is in the range of the heavier nitrogen signatures observed on the lunar surface.     

The non‐igneous genesis of angrites: Support from trace element distribution between phases in D'Orbigny

Abstract— D'Orbigny is an exceptional angrite. Chemically, it resembles other angrites such as Asuka‐881371, Sahara 99555, Lewis Cliff (LEW) 87051, and LEW 86010, but its structure and texture are peculiar. It has a compact and porous lithology, abundant glasses, augite‐bearing druses, and chemical and mineralogical properties that are highly unusual for igneous rocks. Our previous studies led us to a new view on angrites: they can possibly be considered as CAIs that grew to larger sizes than the ones we know from carbonaceous chondrites. Thus, angrites may bear a record of rare and special conditions in some part of the early solar nebula. Here we report trace element contents of D'Orbigny phases. Trace element data were obtained from both the porous and the compact part of this meteorite. We have confronted our results with the popular igneous genetic model. According to this model, if all phases of D'Orbigny crystallized from the same system, as an igneous origin implies, a record of this genesis should be expressed in the distribution of trace elements among early and late phases. Our results show that the trace element distribution of the two contemporaneous phases olivine and plagioclase, which form the backbone of the rock, seem to require liquids of different composition. Abundances of highly incompatible elements in all olivines, including the megacrysts, indicate disequilibrium with the bulk rock and suggest liquids very rich in these elements (>10,000 x CI), which is much richer than any fractional crystallization could possibly produce. In addition, trace element contents of late phases are incompatible with formation from the bulk system's residual melt. These results add additional severe constraints to the many conflicts that existed previously between an igneous model for the origin of angrites and the mineralogical and chemical observations. This new trace element content data, reported here, corroborate our previous results based on the shape, structure, mineralogy, chemical, and isotopic data of the whole meteorite, as well as on a petrographic and chemical composition study of all types of glasses and give strength to a new genetic model that postulates that D'Orbigny (and possibly all angrites) could have formed in the solar nebula under changing redox conditions, more akin to chondritic constituents (e.g., CAIs) than to planetary differentiated rock.     

Light dement geochemistry of the Tagish Lake CI2 chondrite: Comparison with CI1 and CM2 meteorites

Abstract— We have studied the carbon and nitrogen stable isotope geochemistry of a small pristine sample of the Tagish Lake carbonaceous chondrite by high‐resolution stepped‐combustion mass spectrometry, and compared the results with data from the Orgueil (CI1), Elephant Moraine (EET) 83334 (CM1) and Murchison (CM2) chondrites. The small chip of Tagish Lake analysed herein had a higher carbon abundance (5.81 wt%) than any other chondrite, and a nitrogen content (?1220 ppm) between that of CI1 and CM2 chondrites. Owing to the heterogeneous nature of the meteorite, the measured carbon abundance might be artificially high: the carbon inventory and whole‐rock carbon isotopic composition (δ¹³C ? +24.4%_o) of the chip was dominated by ¹³C‐enriched carbon from the decomposition of carbonates (between 1.29 and 2.69 wt%; δ¹³C ? +67%_o and δ¹⁸O ? +35%_o, in the proportions ?4:1 dolomite to calcite). In addition to carbonates, Tagish Lake contains organic carbon (?2.6 wt%, δ¹³C ? ?9%_o; 1033 ppm N, δ¹⁵N ? +77%_o), a level intermediate between CI and CM chondrites. Around 2% of the organic material is thermally labile and solvent soluble. A further ?18% of the organic species are liberated by acid hydrolysis. Tagish Lake also contains a complement of presolar grains. It has a higher nanodiamond abundance (approximately 3650–4330 ppm) than other carbonaceous chondrites, along with ?8 ppm silicon carbide. Whilst carbon and nitrogen isotope geochemistry is not diagnostic, the data are consistent with classification of Tagish Lake as a CI2 chondrite.     

Carbonate abundances and isotopic compositions in chondrites

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ¹³C ≈ 25–75‰ and δ¹⁸O ≈ 15–35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0–130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ¹⁸O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH₄ (δ¹³C ≈ ?33‰ or ?20‰ for CO‐ or CH₄‐dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ¹⁸O ≈ ?5.5‰, and δ¹³C ≈ ?31‰ or ?17‰ for CO‐ or CH₄‐dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10–40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ¹³C ≈ 65–80‰) and less altered samples (δ¹³C ≈ 30–40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (δ¹⁸O ≈ ?9.25‰, and δ¹³C ≈ ?21‰ or ?8‰ for CO‐ or CH₄‐dominated systems, respectively) if the less altered CRs had higher mole fractions of CO₂ in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO₂‐rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO₂ and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO‐dominated fluids to have formed in their parent bodies. If CH₄ was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO₂ when oxidation of metal by water created high partial pressures of H₂. The fact that the chondrite carbonate C/H₂O mole ratios are of the order predicted for CO/CO₂‐H₂O ices that experienced temperatures of >50–100 K suggests that the chondrites formed at radial distances of <4–15 AU.     

Spectral properties of angrites

Abstract— Angrites are generally believed to be fragments of a basaltic asteroid that differentiated under relatively oxidizing conditions. Almost all angrites (e.g., D'Orbigny, Lewis Cliff [LEW] 86010, and Sahara 99555) are composed predominately of anorthite, Al‐Ti diopside‐hedenbergite, and Ca‐rich olivine, except for the type specimen, Angra dos Reis, which is composed almost entirely of Al‐Ti diopside‐hedenbergite. D'Orbigny, LEW 86010, and Sahara 99555 also have spectral properties very different from Angra dos Reis. These newly measured angrites all have broad absorption features centered near 1 μm with very weak to absent absorption bands at ?2 μm, which is characteristic of some clinopyroxenes. The spectrum of Angra dos Reis has the characteristic 1 and 2 μm features due to pyroxene. One asteroid, 3819 Robinson, has similar spectral properties to the newly measured angrites in the visible wavelength region, but does not appear to spectrally match these angrites in the near‐infrared.     

Evidence for high‐temperature fractionation of lithium isotopes during differentiation of the Moon

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low‐Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low‐Ti mare basalts have lower Li contents and lower δ⁷Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high‐Ti mare basalts (δ⁷Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ⁷Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low‐Ti mare basalt 15555, the highest concentrations of Li occur in late‐stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ⁷Li in low‐ and high‐Ti mare basalt sources broadly correlate negatively with ¹⁸O/¹⁶O and positively with ⁵⁶Fe/⁵⁴Fe (low‐Ti: δ⁷Li ≤4‰; δ⁵⁶Fe ≤0.04‰; δ¹⁸O ≥5.7‰; high‐Ti: δ⁷Li >6‰; δ⁵⁶Fe >0.18‰; δ¹⁸O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large‐degree, high‐temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ⁷Li in late‐stage liquids, probably as a consequence of preferential retention of ⁷Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile‐poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ⁷Li ranging between ?2.5‰ and 4‰. The higher δ⁷Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.     

Nitrogen components in IAB/IIICD iron meteorites

Abstract— Isotopic variations have been reported for many elements in iron meteorites, with distinct N signatures found in the metal and graphite of IAB irons. In this study, a dozen IAB/IIICD iron meteorites (see Table 1 for new classifications) were analyzed by stepwise pyrolysis to resolve nitrogen components. Although isotopic heterogeneity has been presumed to be lost in thermally processed parent objects, the high‐resolution nitrogen isotopic data indicate otherwise. At least one reservoir has a light nitrogen signature, δ¹⁵N = ?(74 ± 2)‰, at 900 °C to 1000 °C, with a possible second, even lighter, reservoir in Copiapo (δ¹⁵N ≤ ?82‰). These releases are consistent with metal nitride decomposition or low‐temperature metal phase changes. Heavier nitrogen reservoirs are observed in steps ≤700 °C and at 1200 °C to 1400 °C. The latter release has a δ¹⁵N signature with a limit of ≥?16‰. Xenon isotopic signatures are sensitive indicators for the presence of inclusions because of the very low abundances of Xe in metal. The combined high‐temperature release shows ¹³¹Xe and ¹²⁹Xe excesses to be consistent with shifts expected for Te(n,γ) reaction in troilite by epithermal neutrons, but there are also possible alterations in the isotopic ratios likely due to extinct ¹²⁹I and cosmic‐ray spallation. The IAB/IIICD iron data imply that at least one light N component survived the formation processes of iron parent objects which only partially exchanged nitrogen between phases. Preservation of separate N reservoirs conflicts with neither the model of impact‐heating effects for these meteorites nor reported age differences between metal and silicates.     

H and Cl isotope systematics of apatite in brecciated lunar meteorites Northwest Africa 4472, Northwest Africa 773, Sayh al Uhaymir 169, and Kalahari 009

We have investigated the H and Cl systematics in apatite from four brecciated lunar meteorites. In Northwest Africa (NWA) 4472, most of the apatites contain ～2000–6000 ppm H₂O with δD between ?200 and 0‰, except for one grain isolated in the matrix, which contains ～6000 ppm H₂O with δD of ～500–900‰. This low‐δD apatite contains ～2500–7500 ppm Cl associated with δ³⁷Cl of ～15–20‰, while the high‐δD grain contains ～2500 ppm Cl with δ³⁷Cl of ～7–15‰. In NWA 773, apatites in a first group contain ～700–2500 ppm H₂O with δD values averaging around ～0 ± 100‰, while apatites in a second group contain ～5500–16500 ppm H₂O with δD ～250 ± 50‰. In Sayh al Uhaymir (SaU) 169 and Kalahari (Kal) 009, apatites are similar in terms of their H₂O contents (～600–3000 ppm) and δD values (?100 to 200‰). In SaU 169, apatites contain ～6000–10,000 ppm Cl, characterized by δ³⁷Cl of ～5–12‰. Overall, most of the analyzed apatite grains have δD within the range reported for carbonaceous chondrites, similar to apatite analyzed in ancient (>3.9 Ga) lunar magmatic. One grain in NWA 4472 has H and Cl isotope compositions similar to apatite from mare basalts. With an age of 4.35 Ga, this grain could be a representative of the oldest known lunar volcanic activity. Finally, since numerous evolved clasts in NWA 773 formed through silicate liquid immiscibility, the apatite grains with extremely high H₂O contents, reaching pure hydroxylapatite composition, could provide insights into the effects of such process on the evolution of volatiles in lunar magmas.     

The chlorine isotope composition of iron meteorites: Evidence for the Cl isotope composition of the solar nebula and implications for extensive devolatilization during planet formation

The bulk chlorine concentrations and isotopic compositions of a suite of non‐carbonaceous (NC) and carbonaceous (CC) iron meteorites were measured using gas source mass spectrometry. The δ³⁷Cl values of magmatic irons range from ?7.2 to 18.0‰ versus standard mean ocean chloride and are unrelated to their chlorine concentrations, which range from 0.3 to 161 ppm. Nonmagmatic IAB irons are comparatively Cl‐rich containing >161 ppm with δ³⁷Cl values ranging from ?6.1 to ?3.2‰. The anomalously high and low δ³⁷Cl values are inconsistent with a terrestrial source, and as Cl contents in magmatic irons are largely consistent with derivation from a chondrite‐like silicate complement, we suggest that Cl is indigenous to iron meteorites. Two NC irons, Cape York and Gibeon, have high cooling rates with anomalously high δ³⁷Cl values of 13.4 and 18.0‰. We interpret these high isotopic compositions to result from Cl degassing during the disruption of their parent bodies, consistent with their low volatile contents (Ga, Ge, Ag). As no relevant mechanisms in iron meteorite parent bodies are expected to decrease δ³⁷Cl values, whereas volatilization is known to increase δ³⁷Cl values by the preferential loss of light isotopes, we interpret the low isotope values of <?5‰ and down to ?7.2‰ to most closely represent the primordial isotopic composition of Cl in the solar nebula. Similar conclusions have been derived from low δ³⁷Cl values down to ?6, and ?3.8‰ measured in Martian and Vestan meteorites, respectively. These low δ³⁷Cl values are in contrast to those of chondrites which average around 0‰ previously explained by the incorporation of isotopically heavy HCl clathrate into chondrite parent bodies. The poor retention of low δ³⁷Cl values in many differentiated planetary materials suggest that extensive devolatilization occurred during planet formation, which can explain Earth's high δ³⁷Cl value by the loss of approximately 60% of the initial Cl content.     

Basaltic volcanism on the angrite parent body: Comparison with 4 Vesta

Carbon and nitrogen data from stepped combustion analysis of eight angrites, seven eucrites, and two diogenites, alongside literature data from a further nine eucrites and two diogenites, have been used to assess carbon and nitrogen incorporation and isotope fractionation processes on the angrite parent body (APB), for comparison with volatile behavior on the HED parent body (4 Vesta). A subset of the angrite data has been reported previously (Abernethy et al. 2013 ). Two separate families of volatile components were observed. They were (1) moderately volatile material (MVM), mostly combusting between ~500 and 750 °C and indistinguishable from terrestrial contamination and (2) refractory material (RM), mainly released above 750 °C and thought to be carbon (as ) and nitrogen (as N₂ or ) dissolved within the silicate lattice, fitting with the slightly oxidized (~IW to IW+2) angrite fO₂ conditions. Isotopic fractionation trends for carbon and nitrogen within the plutonic and basaltic (quenched) angrites suggest that the behavior of the two volatile elements is loosely coupled, but that the fractionation process differs between the two angrite subgroups. Comparison with results from eucrites and diogenites implies similarities between speciation of carbon and nitrogen on 4 Vesta and the APB, with the latter being more enriched in volatiles than the former.     

Magnesium isotopic fractionation in chondrules from the Murchison and Murray CM2 carbonaceous chondrites

We present high‐precision measurements of the Mg isotopic compositions of a suite of types I and II chondrules separated from the Murchison and Murray CM2 carbonaceous chondrites. These chondrules are olivine‐ and pyroxene‐rich and have low ²⁷Al/²⁴Mg ratios (0.012–0.316). The Mg isotopic compositions of Murray chondrules are on average lighter (δ²⁶Mg ranging from ?0.95‰ to ?0.15‰ relative to the DSM‐3 standard) than those of Murchison (δ²⁶Mg ranging from ?1.27‰ to +0.77‰). Taken together, the CM2 chondrules exhibit a narrower range of Mg isotopic compositions than those from CV and CB chondrites studied previously. The least‐altered CM2 chondrules are on average lighter (average δ²⁶Mg = ?0.39 ± 0.30‰, 2SE) than the moderately to heavily altered CM2 chondrules (average δ²⁶Mg = ?0.11 ± 0.21‰, 2SE). The compositions of CM2 chondrules are consistent with isotopic fractionation toward heavy Mg being associated with the formation of secondary silicate phases on the CM2 parent body, but were also probably affected by volatilization and recondensation processes involved in their original formation. The low‐Al CM2 chondrules analyzed here do not exhibit any mass‐independent variations in ²⁶Mg from the decay of ²⁶Al, with the exception of two chondrules that show only small variations just outside of the analytical error. In the case of the chondrule with the highest Al/Mg ratio (a type IAB chondrule from Murchison), the lack of resolvable ²⁶Mg excess suggests that it either formed >1 Ma after calcium‐aluminum‐rich inclusions, or that its Al‐Mg isotope systematics were reset by secondary alteration processes on the CM2 chondrite parent body after the decay of ²⁶Al.     

The formation of weathering products on the LEW 85320 ordinary chondrite: Evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites

Abstract— Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the δ¹³C and δ¹⁸O values of the two generations of bicarbonate (Antarctic and Texas) are different: δ¹³C = +7.9‰ and +4.2‰; δ¹⁸O = +17.9‰ and + 12.1‰ respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at ?2 ± 4 °C (Antarctic) and +16 ± 4 °C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapour or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar δ¹³C values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.     

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn (~10–20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ⁶⁶Zn values between 1.7 and 3.7‰ (relative to JMC 3‐0749 Lyon) and δ⁶⁵Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ⁶⁶Zn = ?0.07 to +0.64‰; δ⁶⁵Cu = ?0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ⁶⁵Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen‐poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact‐induced high‐velocity jet of vapor and melts.     

Carbon in howardite,eucrite and diogenite basaltic achondrites

Abstract— The C contents and isotopic compositions of four eucrites, four diogenites and two howardites have been determined. Stepped heating in an O atmosphere was employed to convert selectively different carbonaceous materials to CO₂ gas at various temperatures. This technique successfully distinguishes between terrestrial contaminants and indigenous C. With the exception of the Kapoeta howardite, the howardite, eucrite, and diogenite (HED) meteorites contain ～10–30 ppm indigenous C with δ¹³C between ?29% and ?19%. Kapoeta (a regolith breccia) has an elevated C content and δ¹³C, due to the presence of ¹³C-enriched carbonate minerals (δ¹³C ～ +20%) in CM2- or CR2-like clasts. The range in δ¹³C displayed by HED samples is similar to that of other solar system basalts, such as lunar rocks and Martian meteorites but distinctly different from that of the terrestrial mantle. The diogenites have a slightly lower total C yield and higher δ¹³C than the eucrites, which is a result of degassing of trapped CO/CC₂/CO^2–₃ from the silicate lattice during metamorphism or annealing. However, three out of the four diogenites studied appear to contain a discrete component, possibly of graphitic C coating silicate grains, that is seemingly unaffected by the extended annealing period experienced by the diogenites. It is possible that this component might host the indigenous primitive Xe recently identified in diogenites.     

The Vicência meteorite fall: A new unshocked (S1) weakly metamorphosed (3.2) LL chondrite

The Vicência meteorite, a stone of 1.547 kg, fell on September 21, 2013, at the village Borracha, near the city of Vicência, Pernambuco, Brazil. It was recovered immediately after the fall, and our consortium study showed it to be an unshocked (S1) LL3.2 ordinary chondrite. The LL group classification is based on the bulk density (3.13 g cm^?3); the chondrule mean apparent diameter (0.9 mm); the bulk oxygen isotopic composition (δ¹⁷O = 3.768 ± 0.042‰, δ¹⁸O = 5.359 ± 0.042‰, Δ¹⁷O = 0.981 ± 0.020‰); the content of metallic Fe,Ni (1.8 vol%); the Co content of kamacite (1.73 wt%); the bulk contents of the siderophile elements Ir and Co versus Au; and the ratios of metallic Fe⁰/total iron (0.105) versus total Fe/Mg (1.164), and of Ni/Mg (0.057) versus total Fe/Mg. The petrologic type 3.2 classification is indicated by the beautifully developed chondritic texture, the standard deviation (~0.09) versus mean Cr₂O₃ content (~0.14 wt%) of ferroan olivine, the TL sensitivity and the peak temperature and peak width at half maximum, the cathodoluminescence properties of chondrules, the content of trapped ¹³²Xe_tr (0.317 × 10^?8cm³STP g^?1), and the Raman spectra for organic material in the matrix. The cosmic ray exposure age is ~72 Ma, which is at the upper end of the age distribution of LL group chondrites. The meteorite is unusual in that it contains relatively large, up to nearly 100 μm in size, secondary fayalite grains, defined as olivine with Fa_>75, large enough to allow in situ measurement of oxygen and Mn‐Cr isotope systematics with SIMS. Its oxygen isotopes plot along a mass‐dependent fractionation line with a slope of ~0.5 and Δ¹⁷O of 4.0 ± 0.3‰, and are similar to those of secondary fayalite and magnetite in the unequilibrated chondrites EET 90161, MET 96503, and Ngawi. These data suggest that secondary fayalite in Vicência was in equilibrium with a fluid with a Δ¹⁷O of ~4‰, consistent with the composition of the fluid in equilibrium with secondary magnetite and fayalite in other unequilibrated ordinary chondrites. Secondary fayalite and the chondrule olivine phenocrysts in Vicência are not in isotopic equilibrium, consistent with low‐temperature formation of fayalite during aqueous alteration on the LL parent body. That alteration, as dated by the ⁵³Mn‐⁵³Cr chronology age of secondary fayalite, took place $4.0{}_{?1.1}^{+1.4}$ Ma after formation of CV CAIs when anchored to the quenched angrite D'Orbigny.     

The fate of moderately volatile elements in impact events—Lithium connection between the Ries sediments and central European tektites

Lithium abundances and isotope compositions are presented for a suite of sediments from the surroundings of the Ries Impact structure, paralleled by new Li data for central European tektites (moldavites) from several substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia), including a specimen from the newly discovered substrewn field in Poland. The data set was supplemented by three clay fractions isolated from sedimentary samples. Moldavites measured in this study show a very narrow range in δ⁷Li values (?0.6 to 0.3‰ relative to L‐SVEC) and Li contents (23.9–48.1 ppm). This contrasts with sediments from the Ries area which show remarkable range in Li isotope compositions (from ?6.9 to 13.4‰) and Li contents (0.6–256 ppm). The OSM sediments which, based on chemical similarity, formed the major part of moldavites, show a range in δ⁷Li values from ?2.0 to 7.9‰ and Li contents from 5.8 to 78.9 ppm. Therefore, the formation of moldavites was apparently accompanied by large‐scale mixing, paralleled by chemical and isotope homogenization of their parent matter. The proposed Li mixing model indicates that sands, clayey sediments, and low volumes of carbonates are the major components for tektite formation whereas residual paleokarst sediments could have been a minor but important component for a subset of moldavites. Striking homogenization of Li in tektites, combined with limited Li loss during impacts, may suggest that moderately volatile elements are not scavenged and isotopically fractionated during large‐scale collisions, which is consistent with recent models. In general, whether homogenization of bodies with distinct Li isotope systematics takes place, or collision of bodies with similar Li systematics operates cannot be resolved at present stage but Li isotope homogeneity of solar system planets and asteroidal bodies tentatively implies the latter.     

Populations of nanodiamond grains in meteorites from the data on isotopic composition and content of nitrogen

The present study has shown that the dependence of the isotopic composition of nitrogen on the N/C ratio, revealed from the data for bulk samples of meteoritic nanodiamond, can be obtained within the framework of the following model of the composition of populations of nanodiamond grains: (a) initial nanodiamond, i.e., the nanodiamond in the protoplanetary cloud before the accretion of the meteorite parent bodies, was composed mainly of grains of two populations (denoted as C_N and C_F), the ratio of which changed in meteorites depending on the degree of hydrothermal metamorphism; (b) only the grains of one of these populations (C_N) contain volume-bound nitrogen with δ¹⁵N = ?350‰; (c) the grains of both populations contain surface-bound nitrogen (δ¹⁵N ≡ 0). The calculations revealed the following properties of population grains in this model. (1) The grains of the C_N and C_F populations are most likely the same in isotopic composition of carbon and heterogeneous in distribution of its isotopes: the central part of grains is enriched with the δ¹²C isotope relative to the remainder of the grain. While the value of δ¹³C is ?37.3 ± 1.1‰ for carbon in the central part, it is ?32.8 ± 1.5‰ for the whole volume of the grains. (2) The noble gases of the HL component, specifically Xe-HL, are anomalous in isotopic composition and are most likely contained in the third population of nanodiamond grains (denoted as C_HL), the mass fraction of which is negligible relative to that for other grain populations. Only the grains of the C_HL population have an undoubtedly presolar origin, while the grains of the other nanodiamond populations could have formed at the early stages of the evolution of the protoplanetary cloud material before the accretion of the meteoritic parent bodies.